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This study was intended in paddy (rice husk and rice), sediment, and irrigation water samples taken from the paddy fields of Ergene River, Meriç River, and Yenikarpuzlu Dam reservoir which are frequently grown in the river basin in Thrace region and endosulfan (EN) and PAHs were investigated. For analysis, EN and PAHs were studied by GC-MS. The data obtained as a result of the analyses were compared with the results of the standard reference items, and the accuracy of the results was determined. The standard addition method was used to prove the accuracy of EN and PAHs. The recovery parameters on the extraction efficiency of EN and PAHs were optimized, and the recoveries ranged from 82 to 105%. The methods showed good linearity for EN and PAHs, and the LOD and LOQ for methods were found 0.03–63.1 and 0.1–210 μg kg−1, respectively.
Department of Chemistry, Science and Art Faculty, Kirklareli University, Turkey
Ataturk Soil, Water and Agricultural Meteorology Research Institute, Turkey
Cemile Ozcan*
Department of Chemistry, Science and Art Faculty, Kirklareli University, Turkey
*Address all correspondence to: cemilebal.ozcan@klu.edu.tr
1. Introduction
Industrial and agricultural activities along with increasing industrialization are polluted very quickly of water and soil resources. When these sources of pollution are taken into consideration, it is necessary to follow the industrial and agricultural residues. These pollutants, which are used in agriculture and industry, interfere with the natural environment and threaten the ecological environment. Some pollutants can be found in the environment even after years of prohibition, and others can be transported over long distances. Pollutants are spread to the environment as industrial, agricultural and domestic sources [1, 2].
Direct transport of pesticides on the soil surface or on the plant play a role factors such as evaporation, surface flow, soil penetration and adsorption. Evaporation is on the soil, water and plant surface and the most important factor affecting the evaporation of pesticide is its evaporation pressure. In addition, high temperature, low relative humidity and air movement are environmental factors that accelerate evaporation. Pesticides strongly absorbed by soil particles are much less likely to evaporate [3, 4, 5].
Endosulfan (EN) is an organochlorine and acaricide group. Acute toxicity is a colorless, solid agricultural chemical prohibited due to its bioaccumulative potential and endocrine disrupting effects [4, 5, 6]. EN residues in nature are also known to remain in the soil for at least 6 years [7, 8]. Therefore, it requires examination of the soil contaminated with EN, the product grown in soil, sediment and the water used. Polycyclic systems occur when one ring is sharing two carbons with another ring, or the rings are connected to each other by a C▬C bond [9]. PAHs are from the group of compounds which show unsaturation in molecular formulas and do not give addition reactions which are characteristic for them. In the cyclic structure, PAHs from the class of planar molecules are resistant to oxidation. In addition, PAHs can be found in petrochemical, rubber, plastic, mineral oil, rust oil, paint, leather and other products. Rubber and plastic materials are high-risk materials containing PAH. In the Ergene Basin, where the industry is intense, these compounds are likely to be found. As the molecular weights of PAHs increase, their solubility in water decreases. However, their toxic and carcinogenic properties increase [9, 10, 11, 12]. Contaminated soil, air and aquatic products may also contain PAH. The cooking meat or other food on the grill or at high temperatures increases the amount of PAH in food [11]. In this study, analysis of EN and PAHs compounds shown in Figure 1 was performed.
Figure 1.
Structural formulas of analyzed compounds.
The organic components (PAHs and EN) we analyzed are considered among the primary pollutants [9, 13, 14, 15, 16, 17]. When the pesticides in our ecological environment are taken in high concentration, they can cause deformations on the biological structure of the organism. In the event of prolonged exposure to certain pesticides, cancer can be seen or short-term exposure may result in direct death [13, 15, 16, 17, 18, 19].
The extensively used high sensitivity analytical techniques for the determination of EN and PAHs at low concentrations in environmental samples are GC-MS [6, 8, 20, 21], HPLC-MS [10, 22]. The separation and preconcentration techniques for pesticides are solid phase extraction (SPE) [21, 23, 24], solid phase micro extraction (SPME) [21, 22, 25] and sonication [22, 26], which are used to solve these problems in analysis of EN and PAHs.
The aim of this study was intended in paddy (rice husk and rice), sediment, and irrigation water samples taken from the paddy fields of Ergene River, Meriç River, and Yenikarpuzlu Dam reservoir which are frequently grown in the river basin in Thrace region and EN and PAHs were investigated. Thrace region is a place where industry and agriculture are intense, so the analysis with real examples will be performed of great importance here. For this reason, EN and PAHs, which developed method validation, were studied by GC-MS.
Within the scope of this study, the paddy production areas in the agricultural areas of Thrace Region, direct irrigation from Ergene-Meriç rivers and dam ponds, Ergene and Meriç Basin were evaluated and three regions were determined as the study area. The sampling points are shown in Figure 2. Endosulfan and PAH analyses were made in paddy plant, sediment and irrigation water samples taken from paddy fields, which irrigated from the Ergene River, the Meriç River, and the Yenikarpuzlu Dam Reservoir, considering the distinction of irrigation resources in the rice plants often grown in river basins in the Thrace region. In the Yenikarpuzlu village of Edirne province, around Sığırcı Dam, and from the irrigated area from Edirne-İpsala-Yenikarpuzlu, Edirne-Merkez-Üyüklütatar and Edirne-Uzunköprü-Muhacirkadı Village were collected the paddy, sediment and paddy irrigation water (Figure 2). Endosulfan and PAH analysis were performed method validation by GC-MS.
Figure 2.
Representation of the sampling points on the map.
Agilent GC-MS was used in the determination phase for all studies. The instrument used is the HP-5 MS UI capillary column (30 m × 250μm × 0.25 μm) and the 5990C (Agilent) inert MSD mass detector with 7890A (Agilent) model GC-MS. The electron ionization (EI) system with 70 eV ionization energy in GC-MS, and the He gas was used as carrier gas.
2.1 Preparation of standard solutions
Dilution for Endosulfan (EN) was carried out on pure standard (SIGMA-ALDRICH, Product: 45852, EN solution 100 ng μL−1 in n-hexane, PESTANAL®). As a standard for PAHs, Dr. Ehrenstorfer 2095009 product PAH-mix 9 was used. In the standard, there are mixtures of 16 polycyclic aromatic hydrocarbons (PAHs); naphthalene (NAP), acenaphthalene (ACE), acenaphtylene (ACY), fluorene (FLU), phenantherene (PHN), anthracene (ANT), fluoranthene (FLR), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CRY), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP) and indeno(1,2,3,c,d)pyrene (IcdP). Optimum conditions of EN and PAHs were shown in Tables 1 and 2. According to the mass spectra of the chromatograms of the EN and PAH pesticides, column retention times and ion inputs were studied in SIM mode. Pesticide standards were prepared (0.1, 0.25, 0.5, 1, 2, 2.5, 5, 7.5, 10, 25, 50, 100, 250, 500, 750 and 1000 μg L−1) and measurements were taken. PAH-mix 9 of 16 polycyclic aromatic hydrocarbon compounds in standard contented NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP, and the dilution made out of from standard mixture was prepared standards of 1, 5, 10, and 25 μg L−1. The methods applied in GC–MS for EN and PAHs are given in Tables 1 and 2, respectively.
GC injection conditions
Applied method
Splitless
Injection volume
1 μL
Temperature
250°C
He gas flow rate
1 mL/min
Total flow rate
64 mL/min
Septum cleaning flow
3 mL/min
Temperature program
250°C for 1 min
Cleaning flow for split vent
60 mL/min throughout 2.5 min
Transfer line temperature program
150°C for 0 min, runtime 30 min 280°C for 0 min, runtime 30 min
Column oven temperature program
MS information
Collection mode
Scan
Rate (°C/min)
Temperature (°C)
Standby time (min)
Solvent delay (min)
10.00
Gain factor
5.00
45 (initial)
1
EM voltage obtained
2271
21
150
5
MS source temperature (°C)
230
4
220
0
MS Quad (°C)
150
300 (post run)
3
Scanned mass range
100–279
Table 1.
The optimum GC-MS conditions applied for endosulfan.
GC injection conditions
Applied method
Splitless
Injection volume
1 μL
Inlet temperature
70°C
He gas flow rate
1 mL/min
Total flow rate
64 mL/min
Septum cleaning flow
3 mL/min
Temperature program
300 °C for 1 min
Cleaning flow for split vent
60 mL/min throughout 2.0 min
Transfer line temperature program
150°C for 0 min, runtime 42.43 min 280°C for 0 min, runtime 41.43 min
Column oven temperature program
MS information
Collection mode
Scan
Rate (°C/min)
Temperature (°C)
Standby time (min)
Solvent delay (min)
0.00
Gain factor
5.00
70 (initial)
1
EM voltage obtained
2329
10
120
1
MS source temperature (°C)
230
7
270
13
MS Quad (°C)
150
300 (post run)
3
Scanned mass range
100–279
Table 2.
Optimum GC-MS conditions for PAHs.
The retention times (RT), SIM fragmentation ions, chromatogram programming times of PAHs are given in Table 3. The TICs of EN and PAHs were shown in Figures 3 and 4.
Pesticides
RT (min)
Target ion
Ion 1
Ion 2
Programming time (min)
Naphthalene (NAP)
7.584
128.00
129.00
—
6.00
Acenaphthalene (ACE)
12.394
152.00
153.00
—
8.00
Acenaphtylene (ACY)
13.017
153.00
154.00
—
12.67
Fluorene (FLU)
14.694
166.00
165.00
—
13.50
Phenantherene (PHN)
17.846
178.00
176.00
179.00
15.00
Anthracene (ANT)
17.994
178.00
176.00
179.00
17.91
Fluoranthene (FLR)
21.850
202.00
200.00
203.00
18.10
Pyrene (PYR)
22.556
202.00
200.00
203.00
22.15
Benz(a)anthracene (BaA)
26.650
228.00
226.00
229.00
23.00
Chrysene (CRY)
26.879
228.00
226.00
229.00
26.71
Benzo(b)fluoranthene (BbF)
30.281
252.00
250.00
253.00
26.90
Benzo(k)fluoranthene (BkF)
30.376
252.00
250.00
253.00
30.33
Benzo(a)pyrene (BaP)
37.713
252.00
250.00
253.00
35.65
Benzo(g,h,i)perylene (BghiP)
31.539
276.00
138.00
277.00
31.70
Dibenz(a,h)anthracene (DahA)
38.082
276.00
278.00
279.00
37.95
Indeno(1,2,3,c,d)pyrene (IcdP)
39.436
276.00
274.00
277.00
38.50
Table 3.
The retention times (RT), SIM fragmentation ions, and chromatogram programming times of PAHs.
Figure 3.
GC chromatograms of Endosulfan compound.
Figure 4.
GC chromatograms of PAH compounds.
The standards (EN and PAHs) were prepared in certain concentrations and readings were made in the device and the calibration graphs were plotted to calculate the amounts in the actual samples (Figures 5 and 6).
Figure 5.
The calibration graph of Endosulfan compound.
Figure 6.
The calibration graphs of PAHs compounds.
The linear regression, correlation coefficient, the detection limit (LOD) indicating the performance of the method in the method validation [14], the determination limit (LOQ), relative standard deviation percentage (RSD) and recovery calculations of the pesticides analyzed by GC-MS were shown in Table 4.
Pesticides
Regression equation (linear range)
R2
LOD
LOQ
RSD%
Recovery,%
1
EN
305.77x − 245.32 (1–1000 μg/kg)
0.9999
0.79
2.64
7.39
103
2
NAP
23,096x − 6571.3 (0.25–1000 μg/kg)
0.9984
0.03
0.10
1.85
105
3
ACE
16,398x − 91,561 (1–750 μg/kg)
0.9989
0.23
0.76
1.17
98.9
4
ACY
13,125x − 47,551 (0.5–750 μg/kg)
0.9993
0.05
0.17
0.42
101
5
FLU
11,643x − 78,796 (2.5–750 μg/kg)
0.9985
0.43
1.46
1.62
88.1
6
PHN
13,342x − 98,862 (2.5–750 μg/kg)
0.9978
0.64
2.12
2.17
96.5
7
ANT
6895.2x + 103,892 (2.5–750 μg/kg)
0.9992
1.17
3.89
3.65
100
8
FLR
9819.7x − 70,254 (2.5–750 μg/kg)
0.9981
0.64
2.12
2.28
91.6
9
PYR
9427.9x − 42,495 (2.5–750 μg/kg)
0.9997
0.67
2.24
3.42
97.6
10
BaA
821.31x − 1687.9 (25–750 μg/kg)
0.9995
4.05
13.52
4.96
92.9
11
CRY
1401.4x − 36,903 (25–750 μg/kg)
0.9985
6.78
22.6
1.35
86.9
12
BbF
512.66x − 20,563 (50–750 μg/kg)
0.9986
12.3
40.9
4.86
83.2
13
BkF
504.19x − 23,733 (50–750 μg/kg)
0.9977
17.4
58.1
6.8
84.3
14
BaP
280.02x + 7583.6 (100–1000 μg/kg)
0.9999
20.0
66.3
7.87
82.5
15
IcdP
136.66x − 10,109 (250–1000 μg/kg)
0.9981
63.1
210
3.33
86.1
16
NAP
127.67x − 7342 (250–1000 μg/kg)
0.9991
42.2
141
5.05
90.2
17
ACE
214.46x − 8091.9 (50–1000 μg/kg)
0.9974
14.0
46.7
5.72
95.0
Table 4.
The values of linear regression (y = ax + b), correlation coefficient (R2), LOD (μg/kg), LOQ (μg/kg), and RSD% in the pesticides.
2.2 Collection of samples and preparation for analysis
For each point determined, twice samples were sampled in the months of July (sowing period) and September (harvesting period) in the periods of paddy sowing and harvesting. In the paddy pan, selected for sampling, three points were determined to represent each of the ceilings and pan water, soil and plant samples were made from these points. Since there were no paddy in the sowing period, only in the harvesting period of soil and water “at the latest 5 days before the harvest” were done every triple sampling. The pan water, sediment samples, rice grains and rice husk samples from the paddy samples were coded with the abbreviation “w,” “sd,” “r,” and “rh,” respectively. The coordinates of the locations, code and sampling dates are given in Table 5.
Coordinates
Sowing period
Harvest period
Code
Sampling date
Watering source
Code
Sampling date
Watering source
40°48′25.0″N 26°18′58.9″E
1-w
20.07.2016
Dam Lake
11-w
22.09.2016
Dam Lake
11-sd
1-sd
11-r
11-rh
41°32′19.7″N 26°36′14.4″E
2-w
27.07.2016
Meriç River
22-w
23.09.2016
Meriç River
22-sd
2-sd
22-r
22-rh
41°20′17.8″N 26°52′31.6″E
3-w
02.08.2016
Ergene River
33-w
21.09.2016
Ergene River
33-sd
3-sd
33-r
33-rh
Table 5.
Sampling’s coordinates, codes, and dates.
Water samples prepared for analysis of EN and PAHs are enriched in the solid phase extraction system and prepared for analysis by GC-MS. Plant and sediment samples were enriched with modified QuEChERS method and prepared for analysis by GC-MS. The contents of the solid phase extraction and modified QuEChERS methods are given in Figure 7.
Figure 7.
The enrichment of samples with the solid phase extraction and modified QuEChERS methods.
Along with the developments in industrialization, it has made it necessary to determine organo-contaminant at major and minor levels in the settlements where there is a large amount of factories. In this study, The analysis of EN, NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP were performed in paddy, sediment and water samples taken during paddy planting and harvesting from the places such as Yeni Karpuzlu Dam, Muhacirkadı Village (Ergene River) and Üyüklütatar Village (Meriç River). These analyses were performed by using GC-MS. The results of the analysis of EN and PAHs in samples were given in Tables 6–8.
Sowing period
Harvest period
1Bsd1
1Bsd2
1Bsd3
11Bsd1
11Bsd2
11Bsd3
Dam Basin
EN, mg/kg
31.7 ± 1.7
28.0 ± 2.5
21.8 ± 2.6
17.5 ± 1.3
29.0 ± 2.3
22.5 ± 1.2
NAP, μg/kg
385 ± 30
376 ± 2
325 ± 5
306 ± 8
307 ± 24
314 ± 26
ACE, μg/kg
61.8 ± 2.6
63.7 ± 5.6
62.5 ± 1.9
59.7 ± 4.1
54.7 ± 5.3
53.0 ± 4.6
ACY, μg/kg
264 ± 1
254 ± 14
226 ± 9
208 ± 7
223 ± 10
212 ± 16
FLU, μg/kg
55.6 ± 1.5
70.5 ± 2.9
47.8 ± 2.8
45.1 ± 3.8
53.9 ± 1.3
66.7 ± 2.9
PHN, μg/kg
318 ± 18
263 ± 23
164 ± 13
124 ± 8
113 ± 3
120 ± 5
ANT, μg/kg
485 ± 34
383 ± 35
197 ± 2
122 ± 11
102 ± 6
115 ± 8
FLR, μg/kg
273 ± 10
247 ± 15
236 ± 2
201 ± 14
204 ± 13
204 ± 10
PYR, μg/kg
1867 ± 126
1617 ± 54
1622 ± 55
1265 ± 99
1245 ± 54
1291 ± 48
BaA, μg/kg
708 ± 70
1231 ± 110
1244 ± 95
424 ± 42
497 ± 36
113 ± 7
CRY, μg/kg
1058 ± 75
1190 ± 32
Nd
Nd
Nd
Nd
BbF, μg/kg
970 ± 57
1775 ± 34
Nd
1293 ± 51
1074 ± 48
1118 ± 30
BkF, μg/kg
1359 ± 112
1436 ± 47
900 ± 91
1354 ± 44
1124 ± 49
1163 ± 102
BaP, μg/kg
2462 ± 159
1768 ± 14
2478 ± 121
383 ± 38
1737 ± 119
312 ± 31
IcdP, μg/kg
867 ± 3
968 ± 59
846 ± 42
921 ± 19
758 ± 53
815 ± 58
Meriç-Üyüklütatar Village
2Bsd1
2Bsd2
2Bsd3
22Bsd1
22Bsd2
22Bsd3
EN, mg/kg
27.0 ± 1.7
24.2 ± 1.9
29.9 ± 2.4
36.9 ± 3.6
44.9 ± 2.7
39.7 ± 2.3
NAP, μg/kg
336 ± 22
278 ± 18
321 ± 14
296 ± 12
311 ± 33
254 ± 24
ACE, μg/kg
64.1 ± 1.2
58.5 ± 4.6
58.5 ± 5.1
55.3 ± 4.9
54.6 ± 3.9
50.4 ± 3.1
ACY, μg/kg
248 ± 17
208 ± 16
244 ± 10
249 ± 28
233 ± 5
258 ± 15
FLU, μg/kg
44.6 ± 4.4
44.0 ± 1.9
43.8 ± 3.4
50.3 ± 1.1
39.6 ± 3.9
38.9 ± 0.1
PHN, μg/kg
104 ± 9
126 ± 5
104 ± 12
108 ± 1
69.2 ± 6.1
77.4 ± 3.7
ANT, μg/kg
85.5 ± 3.1
127 ± 9
67.9 ± 5.2
93.7 ± 1.2
21.0 ± 1.3
36.3 ± 3.5
FLR, μg/kg
212 ± 1
212 ± 13
196 ± 13
182 ± 5
156 ± 12
149 ± 11
PYR, μg/kg
1407 ± 61
1415 ± 109
1328 ± 107
1160 ± 17
969 ± 92
881 ± 71
BaA, μg/kg
1115 ± 108
519 ± 7
341 ± 33
749 ± 53
1093 ± 67
154 ± 15
CRY, μg/kg
1136 ± 120
Nd
Nd
Nd
777 ± 69
Nd
BbF, μg/kg
1171 ± 112
1084 ± 99
885 ± 53
1122 ± 109
753 ± 64
661 ± 52
BkF, μg/kg
1427 ± 123
1011 ± 37
368 ± 16
1391 ± 22
801 ± 67
Nd
BaP, μg/kg
136 ± 17
Nd
310 ± 25
160 ± 14
Nd
Nd
IcdP, μg/kg
797 ± 36
777 ± 49
768 ± 95
692 ± 8
Nd
Nd
IcdP, μg/kg
797 ± 36
777 ± 49
768 ± 95
692 ± 8
Nd
Nd
Muhacirkadı-Ergene Basin
3Bsd1
3Bsd2
3Bsd3
33Bsd1
33Bsd2
33Bsd3
EN, mg/kg
21.4 ± 2.2
23.0 ± 1.6
26.5 ± 1.9
33.7 ± 2.5
21.7 ± 2.3
23.3 ± 2.3
NAP, μg/kg
322 ± 12
417 ± 21
408 ± 18
219 ± 19
242 ± 23
226 ± 18
ACE, μg/kg
56.5 ± 3.6
61.5 ± 1.2
56.8 ± 2.6
51.9 ± 2.0
44.1 ± 1.8
57.5 ± 3.4
ACY, μg/kg
232 ± 18
258 ± 12
237 ± 7
235 ± 14
197 ± 19
176 ± 16
FLU, μg/kg
44.6 ± 0.7
48.6 ± 3.8
46.0 ± 1.4
Nd
62.4 ± 2.5
50.7 ± 4.1
PHN, μg/kg
102 ± 6
113 ± 5
77.8 ± 4.7
68.9 ± 6.4
66.7 ± 2.8
101 ± 3
ANT, μg/kg
81.7 ± 6.4
103 ± 9
99.3 ± 2.5
20.3 ± 1.1
27.9 ± 2.1
79.6 ± 6.2
FLR, μg/kg
190 ± 1
137 ± 4
196 ± 14
137 ± 7
245 ± 16
179 ± 5
PYR, μg/kg
1275 ± 72
1314 ± 62
1279 ± 90
790 ± 78
1086 ± 47
1099 ± 52
BaA, μg/kg
659 ± 66
771 ± 78
1549 ± 143
576 ± 41
664 ± 55
570 ± 50
CRY, μg/kg
Nd
Nd
989 ± 91
674 ± 32
521 ± 23
Nd
BbF, μg/kg
1194 ± 28
1014 ± 59
1047 ± 96
Nd
Nd
589 ± 36
BkF, μg/kg
1243 ± 27
580 ± 12
1098 ± 37
Nd
577 ± 32
732 ± 33
BaP, μg/kg
Nd
Nd
Nd
62.0 ± 6.2
483 ± 38
Nd
IcdP, μg/kg
715 ± 28
728 ± 32
708 ± 24
Nd
Nd
Nd
Table 6.
Amount of pesticides in sediment samples in the dam basin, Meriç-Üyüklütatar village, and Muhacirkadı-Ergene Basin (n = 6).
Sowing Period
Harvest Period
1Bw1
1Bw2
1Bw3
11Bw1
11Bw2
11Bw3
Dam Basin
EN, mg/kg
Nd
Nd
Nd
Nd
Nd
Nd
NAP, μg/kg
47.6 ± 4.4
47.3 ± 3.4
58.9 ± 2.9
70.1 ± 0.1
47.2 ± 3.2
105 ± 9
ACE, μg/kg
6.44 ± 0.05
10.3 ± 0.6
Nd
Nd
Nd
Nd
ACY, μg/kg
8.66 ± 0.87
8.76 ± 0.21
9.68 ± 0.48
12.6 ± 0.7
10.3 ± 1.2
13.8 ± 1.1
FLU, μg/kg
7.93 ± 0.78
6.73 ± 3.4
8.07 ± 0.27
6.76 ± 0.14
6.74 ± 0.37
7.70 ± 0.61
PHN, μg/kg
60.6 ± 2.0
104 ± 6
70.4 ± 2.2
44.8 ± 6.1
52.7 ± 1.9
53.8 ± 3.5
ANT, μg/kg
91.6 ± 3.8
18.7 ± 0.7
110 ± 4
62.0 ± 1.9
76.9 ± 3.6
79.0 ± 6.6
FLR, μg/kg
18.2 ± 0.6
65.4 ± 4.2
18.3 ± 0.63
16.2 ± 1.6
17.5 ± 0.6
16.5 ± 0.8
PYR, μg/kg
66.6 ± 4.1
45.0 ± 3.4
62.0 ± 3.1
58.5 ± 0.3
65.8 ± 5.3
55.7 ± 4.2
BaA, μg/kg
45.5 ± 2.3
63.9 ± 3.2
39.6 ± 3.0
34.9 ± 3.4
38.4 ± 3.3
30.5 ± 1.9
CRY, μg/kg
62.0 ± 4.3
Nd
Nd
Nd
60.8 ± 0.8
Nd
Meriç-Üyüklütatar Village
2Bw1
2Bw2
2Bw3
22Bw1
22Bw2
22Bw3
EN, mg/kg
10.6 ± 0.3
Nd
Nd
Nd
Nd
Nd
NAP, μg/kg
47.4 ± 1.1
53.7 ± 4.6
49.2 ± 2.5
39.5 ± 1.8
43.1 ± 2.2
41.1 ± 1.2
ACE, μg/kg
Nd
Nd
6.60 ± 0.01
Nd
Nd
Nd
ACY, μg/kg
8.86 ± 0.71
10.1 ± 0.8
7.86 ± 0.51
9.97 ± 0.13
8.30 ± 0.30
9.10 ± 1.9
FLU, μg/kg
7.24 ± 0.31
8.26 ± 0.47
7.58 ± 0.72
7.41 ± 0.42
6.84 ± 0.26
7.12 ± 0.59
PHN, μg/kg
71.0 ± 2.5
79.1 ± 5.8
69.1 ± 1.1
62.1 ± 4.2
60.8 ± 6.3
61.4 ± 5.3
ANT, μg/kg
111 ± 5
126 ± 10
108 ± 2
94.5 ± 7.9
92.0 ± 7.5
93.3 ± 3.8
FLR, μg/kg
18.4 ± 0.6
20.4 ± 1.2
20.0 ± 1.4
17.2 ± 0.4
16.9 ± 0.6
17.3 ± 1.2
PYR, μg/kg
61.8 ± 2.1
71.8 ± 3.2
75.7 ± 6
51.8 ± 3.7
50.8 ± 3.2
54.1 ± 3.8
BaA, μg/kg
39.3 ± 0.4
44.7 ± 1.9
59.9 ± 4.1
27.4 ± 2.6
26.1 ± 2.1
29.7 ± 2.3
CRY, μg/kg
Nd
Nd
Nd
Nd
Nd
Nd
Muhacirkadı-Ergene Basin
3Bw1
3Bw2
3Bw3
33Bw1
33Bw2
33Bw3
EN, mg/kg
11.1 ± 0.6
7.36 ± 0.63
Nd
8.64 ± 0.32
7.85 ± 0.81
7.99 ± 0.46
NAP, μg/kg
73.5 ± 2.1
53.0 ± 2.7
58.3 ± 3.9
42.4 ± 1.8
38.3 ± 1.1
46.7 ± 4.5
ACE, μg/kg
6.82 ± 0.19
Nd
Nd
Nd
Nd
Nd
ACY, μg/kg
14.8 ± 1.4
14.6 ± 0.69
13.7 ± 1.3
12.7 ± 1.1
10.4 ± 0.8
12.8 ± 1.1
FLU, μg/kg
10.6 ± 0.8
8.84 ± 0.12
9.09 ± 0.74
7.90 ± 0.58
7.41 ± 0.31
8.54 ± 0.52
PHN, μg/kg
93.0 ± 1.4
83.3 ± 2.3
76.3 ± 6.2
76.3 ± 0.9
70.5 ± 6.1
88.4 ± 6.6
ANT, μg/kg
152 ± 9
134 ± 4
121 ± 11
121 ± 2
110 ± 6
144 ± 12
FLR, μg/kg
24.2 ± 1.5
20.6 ± 0.8
19.0 ± 0.7
18.7 ± 0.2
17.5 ± 1.0
16.9 ± 0.1
PYR, μg/kg
92.4 ± 1.6
72.8 ± 5.3
63.0 ± 5.1
61.7 ± 1.6
53.7 ± 4.2
48.7 ± 0.4
BaA, μg/kg
88.3 ± 5.2
43.1 ± 4.1
43.3 ± 2.4
33.3 ± 2.5
30.6 ± 0.9
19.4 ± 0.0
CRY, μg/kg
85.4 ± 2.4
Nd
Nd
Nd
Nd
Nd
Table 7.
Amount of pesticides in water samples in in the dam basin, Meriç-Üyüklütatar village, and Muhacirkadı-Ergene Basin (n = 6).
Rice Harvest Period
Rice Husk Harvest Period
Dam Basın
11Br1
11Br2
11Br3
11Brh1
11Brh2
11Brh3
EN, mg/kg
54.9 ± 4.6
46.4 ± 2.7
54.0 ± 2.8
47.4 ± 0.2
46.7 ± 1.6
41.6 ± 1.7
NAP, μg/kg
220 ± 12
265 ± 18
280 ± 3
679 ± 27
420 ± 29
327 ± 6
ACE, μg/kg
58.3 ± 0.4
55.3 ± 0.9
65.1 ± 2.3
246 ± 6
265 ± 16
239 ± 10
ACY, μg/kg
205 ± 5
246 ± 7
216 ± 2
444 ± 3
374 ± 14
341 ± 6
FLU, μg/kg
71.9 ± 2.8
76.7 ± 2.3
99.0 ± 4.3
62.3 ± 0.4
59.1 ± 0.3
75.2 ± 0.1
PHN, μg/kg
204 ± 4
267 ± 7
192 ± 1
259 ± 18
145 ± 2
181 ± 10
ANT, μg/kg
274 ± 7
396 ± 14
250 ± 2
416 ± 32
157 ± 9
324 ± 7
FLR, μg/kg
179 ± 3
195 ± 1
194 ± 4
145 ± 4
185 ± 4
229 ± 2
PYR, μg/kg
1068 ± 25
1148 ± 12
1142 ± 15
779 ± 20
1080 ± 19
1351 ± 21
BaA, μg/kg
1614 ± 37
1871 ± 86
1770 ± 63
1900 ± 100
2100 ± 17
2760 ± 88
CRY, μg/kg
1101 ± 22
1247 ± 59
1190 ± 30
1247 ± 59
1317 ± 18
1765 ± 58
BbF, μg/kg
Nd
796 ± 79
226 ± 25
961 ± 91
945 ± 93
1303 ± 20
BkF, μg/kg
Nd
Nd
254 ± 24
999 ± 99
1036 ± 103
1253 ± 8
IcdP, μg/kg
1044 ± 73
1101 ± 24
843 ± 7
2076 ± 66
2134 ± 11
2343 ± 51
Meriç-Üyüklütatar Village
22Br1
22Br2
22Br3
22Brh1
22Brh2
22Brh3
EN, mg/kg
53.2 ± 1.4
60.1 ± 3.7
58.4 ± 1.6
43.4 ± 2.8
42.4 ± 3.5
41.8 ± 3.1
NAP, μg/kg
239 ± 7
356 ± 29
383 ± 18
809 ± 23
628 ± 50
882 ± 25
ACE, μg/kg
63.4 ± 0.9
70.5 ± 0.9
60.3 ± 1.5
179 ± 12
150 ± 3
153 ± 7
ACY, μg/kg
194 ± 4
242 ± 7
275 ± 7
403 ± 10
401 ± 12
382 ± 16
FLU, μg/kg
73.7 ± 3.3
51.0 ± 1.5
208 ± 15
105 ± 4
92.5 ± 3.1
102 ± 1
PHN, μg/kg
79.3 ± 1.6
139 ± 7
428 ± 16
179 ± 1
193 ± 3
254 ± 5
ANT, μg/kg
39.6 ± 2.9
172 ± 9
338 ± 26
52.1 ± 5.1
235 ± 6
402 ± 8
FLR, μg/kg
195 ± 4
213 ± 4
228 ± 3
239 ± 8
297 ± 3
270 ± 7
PYR, μg/kg
1176 ± 19
1196 ± 16
1349 ± 18
1436 ± 40
1916 ± 33
1673 ± 48
BaA, μg/kg
1120 ± 52
1478 ± 71
1831 ± 101
2014 ± 79
3788 ± 141
3909 ± 180
CRY, μg/kg
829 ± 25
969 ± 53
1225 ± 67
1330 ± 42
2375 ± 82
2400 ± 123
BbF, μg/kg
215 ± 6
202 ± 3
617 ± 8
950 ± 94
294 ± 29
1261 ± 38
BkF, μg/kg
245 ± 6
261 ± 5
270 ± 26
918 ± 85
537 ± 31
1120 ± 32
IcdP, μg/kg
893 ± 6
948 ± 24
1395 ± 55
2637 ± 80
1426 ± 21
2058 ± 75
Muhacirkadı-Ergene Basin
33Br1
33Br2
33Br3
33Brh1
33Brh2
33Brh3
EN, mg/kg
50.2 ± 2.1
17.7 ± 0.5
28.4 ± 1.5
45.6 ± 1.2
47.2 ± 1.6
41.6 ± 3.2
NAP, μg/kg
285 ± 5
445 ± 34
514 ± 42
603 ± 53
524 ± 36
517 ± 31
ACE, μg/kg
77.0 ± 1.4
55.0 ± 0.2
59.9 ± 0.7
74.9 ± 2.7
94.4 ± 2.2
78.7 ± 4.0
ACY, μg/kg
272 ± 8
331 ± 7
336 ± 23
364 ± 19
337 ± 9
313 ± 12
FLU, μg/kg
250 ± 14
176 ± 4
294 ± 16
268 ± 25
168 ± 13
102 ± 3
PHN, μg/kg
269 ± 22
518 ± 9
336 ± 30
197 ± 4
225 ± 5
189 ± 3
ANT, μg/kg
392 ± 33
859 ± 18
519 ± 15
216 ± 2
199 ± 3
205 ± 8
FLR, μg/kg
222 ± 6
191 ± 4
125 ± 6
358 ± 8
378 ± 7
358 ± 9
PYR, μg/kg
1202 ± 30
1078 ± 32
789 ± 2
2293 ± 36
2576 ± 43
2336 ± 55
BaA, μg/kg
1717 ± 6
1560 ± 67
895 ± 61
2415 ± 46
3766 ± 163
4258 ± 169
CRY, μg/kg
1152 ± 10
1077 ± 37
752 ± 5
1526 ± 44
2413 ± 109
2562 ± 52
BbF, μg/kg
901 ± 75
1029 ± 57
1255 ± 115
1256 ± 127
1042 ± 22
1220 ± 37
BkF, μg/kg
949 ± 48
1403 ± 105
599 ± 22
1722 ± 134
1061 ± 31
929 ± 35
IcdP, μg/kg
1397 ± 24
1531 ± 23
1392 ± 41
2332 ± 96
2300 ± 22
1988 ± 52
Table 8.
The amounts of pesticides in the samples of rice and rice husk in the dam basin, Meriç-Üyüklütatar village and Muhacirkadı-Ergene Basin (n = 6).
Large scale accumulation or pollution of pesticide chemicals or natural chemicals is a source of concern for our global world. Due to the incorporation of these substances into the condensation and evaporation cycle, our natural life creates constant exposure with rain, snow and fog [26]. Soil pollution is closely related to industrial activities, destruction of municipal and industrial waste or environmental accidents. Soil is a complex and heterogeneous matrix with a porous structure containing inorganic and natural organic components [1, 2].
PAH components, which come out from the chemical production factories and vehicles’ exhausts along the Ergene River, constitute a serious source of pollution. In the Ergene Basin is located in petrochemical, rubber, plastic, mineral oil, rust oil, paint, leather and other products. Rubber and plastic materials including PAHs are high-risk materials. For this reason, EN and PAHs analyses of the samples collected from rice cultivated areas in the basin selected as clean region (Yeni Karpuzlu Dam), dirty region (Muhacirkadı Village) and less dirty region (Üyüklütatar Village) were determined. As the molecular weights of PAHs increase, their solubility in water decreases and accumulation in the sediment also increases. When the results obtained are examined, it can be seen that PAHs accumulate in the sediment.
Sampling during the sowing period and harvest period were made classifications as for proximity to the road, and irrigation channel, or proximity to the dam with code of 1B-1 and 11B-1, intermediate zones of 1B-2 and 11B-2, and the more distant area of 1B-3 and 11B-3.
The recoveries for EN and PAHs were ranged from 82.5 to 105%, respectively. The LOD and LOQ for EN and PAHs were found 0.03–63.1 and 0.1–210 μg kg−1, respectively.
The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP and IcdP in sediment samples were found to be 17.5–44.9 mg kg−1, 219–417 μg kg−1, 41.1–64.1 μg kg−1, 176–264 μg kg−1, Nd–70.5 μg kg−1, 66.7–318 μg kg−1, 20.3–485 μg kg−1, 137–273 μg kg−1, 790–1867 μg kg−1, 113–1549 μg kg−1, Nd–1190 μg kg−1, Nd–1775 μg kg−1g, Nd–1436 μg kg−1, Nd–2478 μg kg−1 and Nd–968 μg kg−1, respectively. The pesticide concentrations of BghiP and DahA in sediment samples were found below the limit of determination.
The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, and CRY in water samples were found to be Nd–11.1 mg L−1, 38.3–105 μg L−1, Nd–10.3 μg L−1, 8.30–14.8 μg L−1, 6.73–10.6 μg L−1, 44.8–104 μg L−1, 18.7–152 μg L−1, 16.2–65.4 μg L−1, 45.0–92.4 μg L−1, 19.4–88.3 μg L−1and Nd–85.4 μg L−1, respectively. The sample chromatograms of EN and PAHs in sediment, water, rice and rice husk are shown in Figures 8 and 9. Except for the clean area, EN was determined above the limit of detection in other sampling areas. The amount of EN in the dirty area was determined as ND-11.1 μg L−1. In the Harvest period for the polluted region were found 7.85, 7.99, and 8.64 μg L−1, respectively.
Figure 8.
Endosulfan chromatograms of samples taken from the paddy grown area.
Figure 9.
PAH chromatogram of samples taken from the paddy grown area.
Pesticides strongly absorbed by soil particles are much less likely to evaporate [1, 2, 24]. Since pesticides are more adsorbed in sediment samples, their transition to water decreases. The results were confirmed this. Sodium was found in higher concentrations than sediment samples because of its high solubility in water. This increases the electrical conductivity and reduces the water quality.
The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF and IcdP in rice samples were found to be 17.7–60.1 mg kg−1, 220–514 μg kg−1, 55.0–77.0 μg kg−1, 194–336 μg kg−1, 51.0–294 μg kg−1, 79.3–518 μg kg−1, 39.6–859 μg kg−1, 125–228 μg kg−1, 798–1349 μg kg−1, 895–1871 μg kg−1, 752–1247 μg kg−1, Nd–1255 μg kg−1, Nd–1403 μg kg−1 and 843–1531 μg kg−1, respectively. The pesticide concentrations of BaP, BghiP, DahA in rice samples were found below the limit of determination. The amount of PAHs in the polluted region was more than twice that of the clean region.
The amount of EN, NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF and IcdP in the rice husk samples were found to be 41.6–46.7 mg kg−1, 327–882 μg kg−1, 74.9–265 μg kg−1, 313–444 μg kg−1, 59.1–268 μg kg−1, 145–259 μg kg−1, 52.1–416 μg kg−1, 145–378 μg kg−1, 779–2576 μg kg−1, 1900–4258 μg kg−1, 1247–2562 μg kg−1, 294–1303 μg kg−1, 537–1722 μg kg−1 and 1426–2343 μg kg−1, respectively.
The amount of PAHs in the rice husk samples was found twice the amount of rice. Except for rice and water samples, PAHs accumulation was determined in sediment and rice husk samples.
If we summarize briefly, the BghiP and DahA pesticides in the sediment samples in Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin was be bellowed of limit of detection. It was below the limit of detection of BbF, BkF, BaP, BghiP, DahA and IcdP pesticides content in water samples in the Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin. It was below the limit of detection the BaP, BghiP and DahA pesticides in the rice and rice husk samples in the Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin.
When the results were examined, it was determined that the amounts of pesticides were higher in the samples taken near the Ergene river, but the amounts in the edible section were less than in the rice husk. Rice husk has shown a very good adsorbent and reduced the transport of EN and PAHs in of food. EN and PAHs levels in samples taken from river, stream, or near the canal were found to be higher than the samples taken from the inner sides.
Ergene River Basin surroundings were selected for this study: one heavily contaminated sites, moderately contaminated sites, and one less contaminated reference sites. The modified QuEChERS method used in this study was practical for mixtures found in environmental samples. This technique performs well, exhibiting good sensitivity, selectivity, and precision in the range of concentrations appropriate for the determination of target analytes. Our study investigated to the Ergene River Basin in sediment, rice, rice husk and water were analyzed for trace organic pollutants. However, the sediment and plant (rice and husk) had measurable and sometimes high levels of PAHs, even though no industrial sources of pollution were known. Other sources of PAH contamination may include runoff from paved roads and exhaust from farm machinery, and factory wastes immediate of the sampling stations. Therefore, in the alives feeding with husk of rice, there may be bioaccumulation of EN and PAHs. Ecological risk assessments for the sediment efficacies concluded that response actions were necessary for the sediment and husk, except for water and rice.
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Written By
Barış Can Körükçü and Cemile Ozcan
Submitted: June 30th, 2020Reviewed: July 15th, 2020Published: September 1st, 2020
Open access peer-reviewed chapter
